Long chain alkoxy-diols



LONG CHAIN ALKOXY-DIOLS Harry A. Stanshury, In, South Charleston, and Howard R. Guest, Charleston, W. Va., assignors to Union Carbide Corporation, a corporation of New York No Drawing. Application April 13, 1956 Serial No. 577,942

6 Claims. (Cl. 260-615) where N is the number of alkoxy substituents, and n is the odd number of carbon atoms in the chain.

Long chain diols in which the terminal. hydroxyl groups A are separated by an odd number of carbon atoms have heretofore been unavailable my methods adopted to industrial synthesis. For example, 1,7-heptanediol has been made heretofore by the reduction of diethyl pimelate with metallic sodium by the Bouvealt and Blane method. It has also been isolated in small yields by the hydrogenation of B-furylacrolein. The present invention not only includes a commercially attractive method for making long chain primary diols, but it also provides a novel series of alkoxy-substituted diols. Such alkoxy-substituted diols are of particular value in making polyesters, wherein the alkoxy substituents contribute lower freezing points and increased compatibility with synthetic resins.

The basic raw materials utilized in the new synthesis of long chain alkoxy-substituted diols are acrolein and vinyl alkyl ethers, both of which are available commercially at reasonable costs. In the first step, acrolein is condensed in a known manner with a vinyl alkyl ether to yield a 2-alkoxy-3,4-dihydro-2H-pyran. This pyran is reacted with an alkanol in such a manner as to open the pyran ring and form 1,1,5,5-tetraalkoxypentanes or glutaraldehyde diacetals. These diacetals are then reacted with at least one mole of a vinyl alkyl ether to form diacetals of alkoxy-substituted alpha, omega dialdehydes having at least one alkoxy substituent in the chain and at least seven carbon atoms in the chain. The chain length of thesedialdehyde diacetals increases in increments of two carbon atoms, depending on the number of moles of vinyl alkyl ether reacted, and they contain an added alkoxy group for each increment of two carbon atoms in the chain. These alkoxy-substituted dialdehyde diacetals are then hydrolyzed to the corresponding dialdehydes, which are then hydrogenated to form the long chain alkoxy-substituted diols of this invention.

The various steps of the synthesis are illustrated below:

(I) on on no on CHOR li CH: C

Acrolein Viiuylalkyl no CHOR ether 2-alkoxy-3,4-

2,931,813 7 Patented Apr. 5, 1960 (II) CH: /CE: HO CH: H2O 0H: 2 R OH ii I +ROH+- I HO CHOR ROHC CHOR Alkauol ZallmW-BA- Alkanol 2-6-dialkoxytetrad1hydr0-2H-pyran hydropyran (R0)2CHCH2CH2OH2CH(O R)2+H O 1,1,5,5-tetraalkoxypentane Water III; (RO)zCHCH2Ol-l2CHzGH(OR)2+z(CHz=CHOR)-- 1,1,5,5-tetraalkoxypentane Vinyl alkyl ether 7 ti) R (RO)2CHCH:CH2CH2(CHCH2)=CH(OR),

Acetals of alkoxy-substituted alpha, omega aldehydes.

IV. 0 R

Acetals oi alkoxy-substituted alpha, omega Water aldehydes OR O=CHCH2CH2CH2(CHCH2) =CH=0+ 4ROH Allroxy-substituted dialdehydes Alkanol V. OR

I O=CHCH2CH2CH:(CHCH2) =CH=O+ Alkoxy-substituted dialdehydes Hydrogen a HO CHZCHZCHZCHKCHCH!):OH2OE Alkoxy-substituted terminal diols where x has a value from 1 to 10, depending on the-number of moles of vinyl alkyl ether reacted with the glutaraldehyde diacetal in step III of the synthesis. In the above formula, R is an alkyl radical having from 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl or octyl, and may be the same or different throughout the chain, depending on whether a mixture of vinyl alkyl ethers is used in step iii of the synthesis, and on whether the alkyl radical of the 1,1,5,5-tetraalkoxypentane is the same as or different from the alkyl radical of the vinyl alkyl ether used in the reaction.

While it is possible to isolate definite compounds from the diol mixtures of this invention, such as 3-ethoxy-1,7- heptanediol, the more valuable compositions will comprise mixtures of such diols where x has a value from 1.5 to 5.5.

. In such reactions of the vinyl alkyl ethers with the 1,1,5,S-tetraalkoxypentanes, it is desirable to use an acidic catalyst. Suitable catalysts include boron trifluoride and acid treated clays. The reaction temperatures may be from about 10 C. to about C. with 30 C. to 60 C. being the preferred range. The corresponding reaction pressures may vary from about 5 to 1-50 p.s.i.a.,

with pressures of 15 p.s.i.a. to 50 p.s.i.a.being preferred. The hydrolysis of the alkoxy-substituted acetals to the alkoxy-substitutecl dialdehydes, shown in step IV of the synthesis, is best accomplished at a pH of 1 to 5, with a pH of 2 to 3, being preferred. The hydrolysis temperatures are in the range of 20 C. to 150 C. with temperatures of 80 C. to 100 C. being preferred. Depending on the temperature, the reaction time may vary from a few minutes to as long as 20 hours. The amount of water, used for the hydrolysis may be varied from about 10% of the weight of the acetals to about 500%, with about 100% being preferred.

The longer chain diols when R is ethyl are water-insoluble and are useful as plasticizers and softening agents for polyvinyl alcohol, polyvinyl alkyl ethers, and polyvinyl acetal resins. The water-soluble diols are insect repellents, and have the advantage of ready removal by washing after use.

The alkoxy-substituted diols of the invention are also of value for reaction with phenols to form phenolic materials substituted by the long alkoxy-containing chain of The hydrogenation of the alkoxy-sustituteddialdehydes the diol. These phenolic materials may be reacted with to the alkoxydiols preceeds best at a pH of 3 to 7, with formaldehyde to form phenolic resins having outstanding a pH of 5 to 6 being preferred. The hydrogenation tempropertles as coatings. Thus, on baklng the resin on a foeraturtse may be 56m C. 120111810 C., at presselres surface,-a tough and gextllale film is formed having good mm 1 p.s.i.a. to O p.s.i.a. y rogenation cata yst resistance to water an so vents. u h a R aney nickel or cobalt, is usually employed. 15 The various steps of the synthesis of the diols from The alkoxy-substituted terminal diols of this invention acwlein and Vinyl alkyl Ether-S are i11u5fiaied ifl the are extremely valuable intermediates because the alkoxyamRles to follow, the first p 9 the synthesls, the f substituted carbon chains between the terminal hydroxyl of Y y -PY belrlg groups can be varied from a minimum of seven carbon Show m US Patent atoms to as long as twenty-five carbon atoms. Thus, a 29 PREPARATION OF 1,1,5,5-TETRAALKOXYPEN- proper balance can be maintained in the final derivative TANE-STEP II on, on,

HC on, me on, zonnorr u -c,rr.orr-- C HOH (otmoncrtcmcmcmcH(oc,m ,+mo

0 \0 a-ethe ag dgg droethanol 2,6-dlethoxytetrahydropyran 2,6-diethoxytetrahydropyran Water between the properties contributed by the alkoxy-substi- 3o Example 1 tuted carbon chain and the functional group employed to A mixture of 2760 grams of anhydrous ethanol (60 combine w1th the terminal hydroxyl groups. Thus, the l mo s) and 3.68 grams of 96% sulfuric acid (0.075 equidtols may form a series of polyesters with dibasic acids, valent) was Stirred at 400 C c 768 S of such as succinic, glutaric, adipic, sebacic and azelaic acids, 1 e gram of the formula 2-et hoxy-3,4-drhydro-2H-pyran (6 mols) were fed over a period of 30 minutes. The solution was refluxed for 1 hour to complete the reaction. After 8.2 grams of anll ll H[OZOCYC. ]VZOH hydrous sodium acetate (0.1 equivalent) were added, the where y is an integer having a value from 1 to 10, Y mixture was distilled under reduced pressure to obtain is the alkylene radical of the dibasic acid and has from 2 26'dlehoxytetrahyqmpyran, 43% yleld and to 10 carbon atoms and Z is the residue of the alkoxy- 40 gig g ozxypemane m 53% based on diols having the formula: 1 y

OR v Example 2 l A mixture of 3.68 grams of 96% sulfuric acid (0.075 D d -clrlnontlcmcm(cncnmornh equivalent), 1918 grams of anhydrous ethanol (43 mols) ra ii cf of c a b on a to ii ts io 2ai bo yl gio gs ifi tli pcfiy and i 2 i? z g g r2015) was re uxe or ours. ter grams 0 an y rous esters can be varied over a r g Thus. considersodium acetate were added to neutralize the catalyst, the mg ly the carbon fltomi COHtIIbPted y the Z radlcal, mixture WasfractiOnated under reduced pressure to obtclziegtiescgft e22??? gauging fiatshejedissl ltariJggaggol zy s g fi ilg teiiin 1,1,55-tegaethgigygengne in 51129;; yield and 98% e cienc ase on 1e ox tetra ro a carbon to carbonyl ratios in polyesters improve physical y y y pyr n and chemical stability in the polyesters. Such polyesters CONDENSATION OF. 1,1,5,5-TETRAALKOXYPEN- are valuable plasticizers for vinyl chloride polymers and TANE WITH VINYL ALKYL ETHER'STEP III otheneynthetic resins. By varying the value of x, the (CtHSOMCHCHiCHtCHtCHWC1Hs):+CHt=CH0CeH,-+ ig n tg gl l g'd and compatlblllty of Such polyesters can be 1,1,5,5-tetraethoirypentane vinyl ethyl ether 00 H The polyesters are also of considerable value for form- 2 5 0112 0110 62H! mg polyurethane elastomers having low brittle points by (CamohoHCHCHCHCHCHCHwCH) the reaction of the terminal hydroxyl groups of the poly- 1'13,77'pentaethxyhepmne esters with diisocyanates. Because of the high C/CO 9 001115 ratio eontributed by the long chain diols, such elastomers (C2H50)2CHCH2CH1CHzCHCH:CHCHzCH(O C2Hl 2+ have improved stability to oxidation and hydrolysis. g-hexgethoxynonane Diesters of the alkoxy-substituted terminal diols are 002B OCH readily prepared by acylation of the diols with an alka- 5 z 5 noic acid, such as acetic, propionic, butyric, Z-ethylbu- 65 (CHSO)CHCHCHCHCHCHCHCmemoCHE) tyric, hexanoic and 2-ethylhexoic acids. Such diesters are valuable plasticizers for vinyl chloride polymers. I

The diols of the formula, Example 3 OR 7 (0A mixture of 124 grams of 1,1,5,5-tetraethoxypentane .5 mol) and 52 grams of Superfiltrol (an acid-treated w-here x hasi vzfi g f s fg g i th I d Elayg 0sol'c(l3 by htllre Filtrol Corpgration) was stirred at 25 e e ow a nu w en 1s e y an w ie a solution 0 144 grams of vinyl ethyl Sign; ribgletf :1 LVSITZ2151itngliilhitsgfgflxliliilgsoluble and gather mols)fig 248 grams ofdl,laitetraethoxy xgitane ms, as coumo was e over a perto 0 minutes. ter a plmg agents in water-based emulsions, and as humectants. reaction period of half an hour at 25 C., the mixture was filtered. The filtrate was mixed with 5 grams of potassium carbonate (to neutralize traces of acid) and dlstllled to obtain the following product fractions:

Equivalent Weight as Acetal S G. Fraction Boiling Range 28/20 N 30/D Example 4 A mixture of 1.6 grams of 47% boron trifluoride diethyl ether (0.033 equivalent) and 303 grams of 1,1, 5,5-tetraethoxypentane (1.22 mols) was stirred at 35- 40 C. while a solution of 432 grams of vinyl ethyl ether (6 mols) in 744 grams of 1,l,5,5-tetraethoxypentane (3 mols) was fed over a period of one hour and forty minutes. After a reaction period of 45 minutes at 35 C., 5.3 grams of powdered anhydrous sodium carbonate (0.1 equivalent) were added and the mixture was stirred for 2 hours at 30 C. The mixture was filtered and the filtrate was flash-distilled (in the presence of grams of sodium carbonate) to a kettle temperature of 248 C.

at a reduced pressure of 4 mm. The residue (437 grams) had an equivalent weight of 344 by acetal analysis.

The flash-distilled product fraction (514 grams) was fractionated to isolate the following fractions:

Equivalent Sp. G. Fraction Boiling Range Weight as 20120 n30/D Acetal 143 153" 0J3 mm 166.5 Y 0. 92s 9 1.4258 15s-1s3 (1.13 mm 136. 0 0. 933 1. 42s? 163-115 C./3 mm 201. 0 0. 937 1. 4308 175-212 O. 3 221. 0 0. 943 1. 4350 Fraction 1 was 1,1,3,7,7-pentaethoxyheptane, fraction 2 was a mid-cut, fraction 3 was a mixture of 1,1,3,5,9,9- hexaethoxynonane and the isomeric 1,1,3,7,9,9-hexaeth xynonane and fraction 4 was mostly the latter 1S0- meric mixture. The yield of 1,1,3,7,7-pentaethoxyheptane was and the yield of hexaethoxynonane was based on 1,1,5,5-tetraethoxypentane.

PREPARATION OF ALKOXY SUBSTITUTED DIALDEHYDESSTEP IV 1,1,5,5-tetraethoxypentane vinyl ethyl ether 0 02115 21120 (CZH50)2CHCH2CHZGH2 CHCH; zCH(oCZH5)T polyethoxytetraethyl acetals acid 0 0 2H: O=CHCHCHCH2 CHCH2 eCH=O+4C2H OH polyethoxydialdehydes ethanol Example 5 A mixture of 992 grams of 1,1,5,5-tetraethoxypentane (4 mols) and 40 grams of Superfiltrol (dried at 200 C. for 17 hours) was stirred at 45 -50 C. while a solution of 864 grams of vinyl ethyl ether (12 mols) in 1984 grams of 1,1,5,5-tetraethoxypentane (8 mols) was fed over a period of 2.5 hours. After a reaction period of 2 hours at 50 C., the mixture was cooled and filtered. The filtrate was stripped (in the presence of 35 grams of anyield and efiiciency based on vinyl ethyl ether were 82% and respectively.

The above polyethoxytetraethyl acetal (1724 grams, 8.72 equivalents) was mixed with an equal weight of water and 33 ml. of 0.5 N sulfuric acid were added to reduce the pH to 3. The mixture was distilled with reflux for 5.5 hours until no more ethanol was being generated. Analysis of the aqueous ethanol distillate (967 grams) showed that it was 83% ethanol, which corresponded to a quantitative yield of, ethanol based on the acetal charged. The residue was separated into 803 grams of oil layer which contained 4.37 equivalents of aldehyde and 1686 grams of water layer which contained 3.18 equivalents of aldehyde by analysis. The yield of dialdehydes based on the tetraethyl acetals was 86.6%.

Example 6 ing n 30/D 1.4340, sp. g. 20/20 0.944, 214 equivalent weight by acetal analysis. The yield and efiiciency based on vinyl ether were 82% and 90%, respectively. The yield and efiiciency based on 1,1,5,5-tetraethoxypentane were 66% and 90%, respectively.

The polyethoxytetraethyl acetal (2530 grams, 214 equivalent weight, 11.82 equivalents, x=2.5 in the general formula) was distilled with 1250 ml. of water containing 25 ml. of 0.5 N sulfuric acid to reduce the pH to 2. After 8 hours, 1313 grams of aqueous ethanol had been distilled and no more ethanol was being formed. The residue was separated into 1653 grams of oil layer which contained 10.8 equivalents of aldehyde and 801 grams of aqueous layer which contained 0.662 equivalent of aldehyde by analysis. The yield of dialdehydes based on the acetals was 97% Example 7 A mixture of 1948 grams of polyethoxytetraethyl acetals (192 equivalent weight, x=2.03, 10.15 equivalents) was distilled with 1948 ml. of water containing 30 ml. of 0.5 N sulfuric acid to reduce the pH to 3. After 6 hours, 1199 grams of distillate containing 20.6 mols of ethanol had been collected and no more ethanol was being liberated. The residue was separated into 914 grams of oil layer containing 6.12 equivalents of aldehyde and 1758 grams of aqueous layer containing 3.30 equivalents of aldehyde by analyses. The yield of dialdehydes was 93% based on the acetals.

PREPARATION OF ALKOXY SUBSTITUTED TERMINAL DIOLSSTEP V (O C2115 O=CHCHQCH2CH2 CHCHZ zC1E[=O+2Hf polyethoxydialdehydes hydrogen (00.115 HOCHzCHzCHz JHCHi ,CHzOH polyethoxydiols '7 7 Example 8 The polyethoxytetraethyl acetals were prepared as preyiously described to obtain a residue product having an equivalent weight of 192.6, with x=1.91 in the above 8 residue product had'these properties: 11 307D. 1.4346, sp. g. 20/20 0.942, 260 equivalent Weight by acetal analysis. The yield and efiiciency were '45 and 81%, respectively, based on 1,1,5,5-tetraethoxypentane. The

formula. This acetal mixture was hydrolyzed as previfij g gg i g fi g zg 85% and respectwely ously described to produce the dialdehydes in 95% yield. y y

The above acetal (x=3.78 1n the general formula) was The resulting layers (containing 4.11 equivalents of aldeh dr 1 d S reviousl described to mdu th (fame hyde) were treated with 20 ml. of 2% sodium hydroxide y o a P y p Ce 6 hydes 1n 94% yield. The neutrahzed aqueous mixture (to increase the pH to 6) and hydrogenated 1n the pres- 10 of dialdehydes was hydrogenated in the presence of 5% ence of 5% by welght of Raney nlckel. The filte1ed b y we1ght of Raney nlckel catalyst. The filtered product product was fractionated to obtam 3-ethoxy-l,7-heptaneo was stripped to a kettle temperature of 75 C./ 12 mm. (1101 (x 1 1n the above formula) having these proper- .s D to obtam a residue product having these properties. ties, bolllng range 150 170 C./3 mm, n 30/D 1.4567,

/20, 1000 92 1 t w i ht b h d ox 1 n /D 1.4581, sp. g. 20/20 0.998, 181.5 equivalent eq 1 3 en eg y r y 15 weight by hydroxyl analysis, 336 molecular weight by Emmi/5.15 (theory 180 molecular welght by the the Menzies-Wright method, insoluble in water. The gi g i fgg g2 g g"y 2 :Z g ztg yield of diol was 80% based on the dialdehyde charged. The higher boiling iii-actions had the properties recorded Example 11 below: A mixture of 372 grams of 1,1,5,5-tetraethoxypentane Bolling Misclble Fraction Range Mol. Eq. n30/D Sp.G. Percent Percent with at a C Wt. W 20l20 G H Water mm.,

1 170-190 216 115 1.4010 1.030 61.8 11.3 1.54 Yes. a 190-240 310 163 1.4614 1.000 61.9 12.9 2.86 No.

1 Determined by the Menzies-Wright method. 1 Determined by analytical phthalntion. 3 Calculated from the observed molecular weight.

All but 5% of the product was distilled. The yield (1.5 mols) and 24 grams of Superfiltrol (dried at 200 of diols was 80% based on the dialdehyde charged. C.) was stirred at 500 C. while a solution of 744 grams Example 9 of l,1,5,5-tetraethoxypentane (3 mols) in 1296 grams of vin leth l eth 18 mol as f d o d of A11 aqueous mixture of p y y ydes having 2.6 hci urs. After a reaction pri'iod of g l io in eif 50 an equivalent weight of 113 p p as P C., the mixture was filtered. The filtrate was stripped viously described, WES treated sodium hydroxide (in the presence of grams of anhydrous sodium car. 10 increase the P t0 The mixture was hydrogenated bonate) ,to a kettle temperature of 180 C./3 mm. The 1 0P e (i2 of Raneyhnickeldto tempii l t m g filtered residue product had these properties: 11 30/D 0 at P- 6 P was ere 1.43.81, sp. g. 20/20 0.947, 379 equivalent weight by and ipp to kettle tempefatur? 0f 7 acetal analysis. The yield and efiiciency were and 111:: Obtam a 1 f gi/g i lggg pgg z g l g l o 67%, respectively, based on 1,1,5,5-tetraethoxypentane. 1 e56 P P P- a The polyethoxytetraethyl' acetals described abovev 161.5 equivalent weight by hydroxyl analysis, miscible =7 1 i th general formula) were hydrolyzed as i a t iifs Z2321iiiiilfii ivl fitinlifi i t??? i ilt i? 0 W 1 P t e 1a e y es. ter neutraization o te aci catarotor type of molecular still to obtain the following fracl h mixture was h d o d i th presence f trons: 5% Raney nickel catalyst at 1000 p.s.i.g. to a maximum temperature of 150 C. The filtered product was ct 12 221: 1x12555555 gr ag s nae/D x2 stripped to a kettle temperature of 85 C./12 mm. to

Q Weight, obtain a mixture of polyethoxydlols havlng these properties: n 30/D 1.4551, sp. g. 20/20 1.002, 264 equiv- 100 200 16 1 4582 alent weight by hydroxyl analysis, 455 molecular weight as 13 21: 1.25% g f; by the Menz1es-Wr1ght method, lnsoluble 1n water. The Egg 2% {252% $3,118 Z'gg 23,33 yield of diols was 89% based on the acetals. Rpeidnp 4'2 296.0 6.78 815.0 Example 12 "91 I (CHaO)1CHCHgCH:CHzCH(OCHa)z+xCHz=CHOCHa- 1 Determined by analytical phthalation. 1,1,5,5-tetramethoxypentane vinyl methyl ether I The a\ eruge value of z in the general formula as calculated from the O CH observed equivalent weight.

3 Determined by the Menzies-Wright method. I (CH=0):CHCHQCH:CH2($HCH2):CH(O CHI) This distillation shows that only about 5% of the resipolymethoxytetramethyl acetals due product could not be distilled.

Example 10 A mixture of 1056 grams of 1,1,5,5-tetramethoxypen- A 1 rm f 115 St t th t ti t is and 20 ti s is t i 1 g i mlX 0 gl'ams 0 1 e we xyp n 3116 in let y et er was stirre at 5- w ie (3 mols) and 37 grams of Superfiltrol (dried at 200 grams of gaseous vinyl methyl ether (5.35 mols) were C.) was stirred at 50 C. while a solution of 1296 grams fed over a period of 2.8 hours. After a reaction period of vinyl ethyl ether (18 mols) in 1488 grams of l,1,5,5- of an hour at 30 C., the catalyst was neutralized by the tetraethoxypentane (6 mols) were fed over a period of addition of excess anhydrous ammonia. The product 3.2 hours. After a reaction period of 2.5 hours at 50 was stripped to a kettle temperature of 156 C./5 mm. C., the mixture was filtered and distilled (in the presto obtain a residue product having sp. 1;. 20/20 1.005 ence of 32 grams of pulverized sodium carbonate) to and 161 equivalent weight by acetal analysis. This cora. kettle temperature of 192 C./2 mm. The filtered responds to an average value of x=2.24 in the above (C H50) :CHC H2CHaCHz CHCHz) =CH(O CH:)a+2H:O-

polymethoxytetrarnethyl acetals O C H:

=CHC H,OHgCH1( C HCH2) ,CH=O +4CH=OH polymethoxydialdehydes methanol OCH:

HO 011,0mcm'cnxbncmlcmon polymethoxydiols A mixture of 911 grams, of polymethoxytetramethyl acetals (5.65 equivalents, x=2.24), 911 ml. of water and 25 ml. of 0.5 N sulfuric acid (to reduce the pH to 2.5) was distilled over a period of 5.5 hours to exhaust all the methanol from the system. The residue was separated into 467 grams of oil layer containing 3.30 equivalents of dialdehydes and 836 grams of aqueous layer containing 2.07 equivalents of dialdehydes. The yield of polymethoxydialdehydes was 95% based on the acetals.

One half of each layer of dialdehyde solution described above were mixed and treated with 24 ml. of 0.5 N sodium hydroxide to increase the pH of the mixture to 5.5. The resulting mixture was hydrogenated in the presence of 34 grams of Raney nickel to a maximum temperature 150 C. and 1000 p.s.i.g. The filtered product was distilled to obtain the diol fractions described in Table I. By comparison to the theoretical values for the first three members of this series of diols given in Table II, it may be seen that these were the principal products.

1O PREPARATION OF PQLYESTERS" OCzHs HOCHzCHnCHzCITz CHCH2 :CHZOH+ HOOCCHrCHzCHaCHzCOOH--v polyethoxydiols adipic acid zHs O --0CHQCH2CH2CH1 $HCH2 CH2OOCCH2CHzCH1CH3 -f-2H 0 polyester 7 water Example 13 Adipic acid was esterified with a 10% excess of three different mixtures of polyethoxydiols by refluxing at 175185 C. in the presence of xylene until no more water was being formed. The mixture was stripped to a kettle temperature of 175 /5 mm. to obtain the polyesters as residue products having the properties recorded below. The yields were almost quantitative in each experiment.

Polyester Properties Experiment Eq. Wt.

Number of Diol I Mixture 1 n30/D M01. Acidity 1 De ermined by analysis for hydroxyl groups.

2 Calculated from the equivalent weight of the diol mixture.

3 Ml. of 1.0 NKOH per gram.

4 Deermined by the Meuzies-Wright method as modified by Hill and Brown [Analytical Chemistry 22, 562 (1950)].

A mixture of 1 part of polyester and 3 parts of dioctyl phthalate was compatible with a vinyl chloride-acetate copolyrner containing 97% vinyl chloride at 41% plasti- TABLE I Boiling Mlselble Percent Fraction Range, Eq. M01. 2 3 Percent Percent n30/D Sp. G with 01' Stlll O./ Wt. Wt. C H 20/20 H O? Charge 3 mm.

1 116.0 158.5 0.95 58. 4 11.4 1.4525 1.010 Yes 18 111. 3 174. 7 1.22 60.6 11. 6 1.4620 1. 020 Yes. 28 114. 4 203. 5 1. 71 60. 3 10. 8 1. 4658 l. 035 Yes 18 2-271- 153.] 287. 5 3. 16 62. 3 10. 6 1. 4761 4 1. 038 Yes. 17 Residue NO 19 1 Determined by hydroxyl analysis. Determined by the Menzies-Wright method. 3 Calculated from the observed molecular weight. 4 Taken at 40 C. I

TABLE II cizer concentration. This plasticized composition had excellent permanence because of low volatility and low 2 E Wt. M01. Percent Percent 9 wt 0 H 011 extraction.

' V PREPARATION OF DIESTERS 81 162 59. a 11. 1 n 110 220 60.0 10.9 139 218 198 noomomcmom CHCH: =CH2OH+2CH3(CH2)4COOH polyethoxydiols hexanoic acid The two other halves of the dialdehyde layers described above were mixed and treated with 26 ml. of 0.5 N sodium hydroxide to increase the pH to 5.5. This mixture was hydrogenated in the presence of 34 grams of Raney nickel to a maximum pressure of 150 C. and 1000 p.s.i.g. The filtered solution was stripped to a kettle temperature of 70 C./1 mm. to obtain a residue product having these properties: it 30/D 1.4692, sp. g. 25/ 20 1.039, 115.5 equivalent weight by hydroxyl analysis, 204.1 molecular weight by the Menzies-Wright, miscible with water. The yield of diols was 82% based on the dialdehydes. The average value for x in this residue product was 2.19 based on the hydroxyl analysis. while the value was 1.73 based on' the observed molecular weight.

O CaHg Example 14 A mixture of 139 grams of distilled polyethoxydiol (1.0 equivalent, fraction 3 of Example 9), 232 grams of hexanoic acid (2.0 equivalents), 300 ml. of toluene and 1 ml. of concentrated sulfuric acid (0.0375 equivalent) was refluxed an hour at atmospheric pressure While the water liberated was collected in a decanter. The residue was treated with 3.5 grams of anhydrous sodium acetate (0.4 equivalent) and stripped to a kettle temperature of 145 C./1 mm. The residue was washed with 250 ml. of water at 60 C. (to remove salts) and ml. of heptane were added to aid the separation of layers. The oil layer was stripped to a kettle temperature of 140 C./ 2 mm. to obtain the esters as a residue product having sp. g. 20/20 '11 0.956, n 30/D 1.4439. 1.8% acid as hexanoic, 219 equivalent weight as ester, 413 molecular weight by the Menzies-Wright method. The yield was. almost quantitative.

This ester mixture was compatible at 40% concentration in vinyl chloride-vinyl acetate copolymers.

Example 15.PoIyurethane elastamers Adipic acid (146 grams), polyethoxydiols (molecular weight 336, equivalent weight 181.5, x=3.22 based on molecular weight) (320 grams), and ethylene glycol (12.4 grams) were heated at 160 C. for 26 hours. The reaction temperature was then increased to 190 C., and a vacuum of 10 mm. was applied for 3.5 hours. The resulting polyester had a hydroxyl number of 46.7, a carboxyl number of 8.4, and a molecular weight of about 1770.

This polyester (250 grams) was then reacted with 3,3- dimethyl-4,'4-biphenylene diisocyanate (56 grams) at 120-140 C. for 15 minutes. Ethanolamine (5.2 grams) was then added and the mixture was stirred until an elastomeric gum-stock was obtained.

To a portion of the above gum-stock, 7 percent by weight of 3,3'-dimethyl-4,4'-biphenylene diisocyanate was added on a cold rubber mill. The resulting mixture was molded into a test specimen of 0.07 inch thickness by moldingunder pressure for 15 minutes at 160 C. The cured elastomer exhibited the following physical properties:

Example 16.Mdified phenolic resins The following charge was placed in a three-necked flask fitted with condenser, air stirrer and thermometer.

grams Polyethoxydiols: HOCHzCHzCH2CH2(CH-CH2)zCHrOH (equivalent weight, 189.6; molecular weight, 295.0;

x=265) 24 grams phenol 9.5 grams zinc chloride The material was stirred vigorously and heated at 160 C. for 6 hours after which time the flask was cooled and the material was washed with warm water several times. A solution was made in methanol and activated charcoal was used to remove some of the color. After filtering the methanol solution was steam distilled and the residue was dried at 50 C. for 24 hours in a forced air ovcn. Seven grams of a dark brown solid which showed 45.6% phenol by analysis was recovered.

Five grams of the above solid was dissolved in 20 grams of ethyl alcohol/toluene (50/50) and 3.6 grams of formalin and 0.1 gram of potassium hydroxide were added to the solution. This mixture was stirred for 7% 12 hours atroom temperature after which time a film was dip coated from the'solution onto a 1" x 4" iron panel. The panel was baked for 1 hour at 200 C. and the resulting coating on testing showed good flexibility, strength, solvent resistance (5 min. boiling pyridine) and waterresistance (1 hour boiling water).

What is claimed is: 1. Mixtures of the group consisting of alkoxy-substituted alpha, omega primary diols of the formula HOCHICHzCHzCH: HCHz :CHaOHi where R is an alkyl radical having from 1 to 8 carbon atoms and x has an average value from 1.5 to 10.

2. A mixture of alkoxy-substituted alpha, omega pri mary diols of the formula V HOCHzCHzCHzCH, CHCH2 CH2OH where R is an alkyl radical having from 1 to 8 carbon atoms and x has an average value from 1.5 to 5.5.

3. The compositions of claim 2 where R is methyl. 4. The compositions of claim 2 where R is ethyl. 5. A mixture of water-insoluble ethoxy-substituted alpha, omega primary diols of the formula HOCHzCHzCHzCH: CECE: zCHiOH where R is ethyl and x has an average value'from 2 to 10.

6. A mixture of water-insoluble methoxy-substituted alpha, omega primary diols of the formula (on HOCHzCHzCHaCHa CHCH; :CHzOH where R is methyl and x has an average value from 4 to 10.

References Cited in the tile of this patent UNITED STATES PATENTS 2,487,525 Copenhaver Nov. 8, 1949 2,502,433 Copenhaver Apr. 4, 1950 2,514,168 Smith et al. July 4, 1950 2,556,312 Young June 12, 1951 2,575,195 Smith et al Nov. 13, 1951 2,587,904 Ryan .1. Mar. 4, 1952 2,600,275 Smith June 10, 1952 2,618,663 Glickman Nov. 18, 1952 2,622,101 Paul et al. Dec. 16, 1952 2,623,906 Gresham Dec. 30, 1952 2,654,775 Bell et a1. Oct. 6, 1953 2,691,663 Smith Oct. 12, 1954 2,691,684 Frevel et al Oct. 12, 1954 2,704,771 Smith Mar. 22, 1955 2,768,976 Weidlich et al. Oct. 30, 1956 FOREIGN PATENTS 698,736 Great Britain Oct. 21, 1953 OTHER REFERENCES Curme et a1.: Glycols (1952), pp. 284-299. 

1. MIXTURES OF THE GROUP CONSISTING OF ALKOXY-SUBSTITUTED ALPHA, OMEGA PRIMARY DIOLS OF THE FORMULA 